Organometallic Mn(I) Complexes in Asymmetric Catalytic (Transfer) Hydrogenation and Related Transformations

ChemCatChem, Год журнала: 2024, Номер 16(14)

Опубликована: Март 7, 2024

Abstract Direct asymmetric hydrogenation (AH) and transfer (ATH) are among the most efficient approaches to produce chiral building blocks. Recently, these types of transformations have witnessed a shift towards use molecular catalysts based on earth‐abundant transition metals due their ready availability, economic advantage, novel properties. With particular regard manganese, catalyst development has seen both efficiency substrate scope in AH ATH greatly improved, with emergence large number well‐defined Mn‐complexes employed this field. The reaction includes C=O bonds, reduction C=N bonds reductive C=C bonds. Herein, our survey area focuses catalytic activity such complexes, versatility routes convert substrates target molecules. We consider collected findings article will be helpful reader by providing an insight into ligand design, thereby aiding future development. Moreover, review is aimed at highlighting remarkable progress made last seven years manganese complexes for enantioselective reduction.

Язык: Английский

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Cycloheptyl-fused-PNN-manganese catalyzed asymmetric transfer hydrogenation of ketones

Molecular Catalysis, Год журнала: 2024, Номер 564, С. 114274 - 114274

Опубликована: Июнь 8, 2024

Язык: Английский

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The importance of alkali cations in manganese-catalyzed enantioselective transfer hydrogenation of ketones: An insight into the effect of “NH” and “C N” groups in ligands

Journal of Catalysis, Год журнала: 2025, Номер unknown, С. 115998 - 115998

Опубликована: Фев. 1, 2025

Язык: Английский

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Selective Transfer Hydrogenation of C=O and Conjugated C=C Bonds Using An NHC‐Based Pincer (CNC)Mn^I Complex in Methanol**

ChemSusChem, Год журнала: 2023, Номер 16(18)

Опубликована: Июнь 8, 2023

Base metal catalyzed transfer hydrogenation reactions using methanol is highly challenging. Employing a single N-heterocyclic carbene (NHC)-based pincer (CNC)MnI complex, chemoselective and double of α, β-unsaturated ketones to saturated or alcohols by utilizing as the hydrogen source disclosed. The protocol was tolerant towards selective C=C C=O bonds in presence several other reducible functional groups led synthesis biologically relevant molecules natural products. Notably, this first report Mn-catalyzed carbonyl with methanol. Several control experiments, kinetic studies, Hammett density theory (DFT) calculations were carried out understand mechanistic details catalytic process.

Язык: Английский

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Enhancing enantioselectivity of manganese catalyst for asymmetric transfer hydrogenation of ketones through P,N,N-chelation of a cyclooctyl pyridine

Journal of Catalysis, Год журнала: 2024, Номер 437, С. 115682 - 115682

Опубликована: Июль 31, 2024

Язык: Английский

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Chiral P,N,N‐Ligands for Asymmetric Hydrogenation

Advanced Synthesis & Catalysis, Год журнала: 2024, Номер 366(10), С. 2165 - 2185

Опубликована: Апрель 9, 2024

Abstract The chiral P,N,N‐ligands represented a new type of tridentate ligand developed in recent years and displayed wide utilities asymmetric catalysis. In the past decades, numerous with ferrocene, phenethylamine spiro backbones were synthesized by addition an aminopyridine, imidazole or diamines coordinating group. These showed excellent performance ruthenium, iridium, manganese, cobalt‐catalyzed hydrogenations. A range substrates, including simple ketones, α‐halogenated α‐hydroxy α‐ β‐amino keto‐ ones, α‐, γ‐, δ‐keto acids, β‐keto amides, β‐ esters, β‐enones, olefins, imines, quinolines indoles, could be hydrogenated to afford corresponding products high yields enantioselectivities. this review, progress on hydrogenation C=O, C=N, C=C bonds was summarized.

Язык: Английский

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Enantioselective synthesis of chiral β-hydroxy sulfonesviamanganese catalyzed asymmetric hydrogenation

Organic Chemistry Frontiers, Год журнала: 2023, Номер 10(13), С. 3321 - 3327

Опубликована: Янв. 1, 2023

The first example of manganese catalyzed asymmetric hydrogenation β-keto sulfones for the construction chiral β-hydroxy with up to 97% yield and ee.

Язык: Английский

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Hydrogenation of Terminal Alkenes Catalyzed by Air‐Stable Mn(I) Complexes Bearing an N‐Heterocyclic Carbene‐Based PCP Pincer Ligand

Chemistry - A European Journal, Год журнала: 2023, Номер 30(4)

Опубликована: Окт. 10, 2023

Efficient hydrogenations of terminal alkenes with molecular hydrogen catalyzed by well-defined bench stable Mn(I) complexes containing an N-heterocyclic carbene-based PCP pincer ligand are described. These reactions environmentally benign and atom economic, implementing inexpensive, earth abundant non-precious metal catalyst. A range aromatic aliphatic were efficiently converted into alkanes in good to excellent yields. The hydrogenation proceeds at 100 °C catalyst loadings 0.25-0.5 mol %, 2.5-5 % base (KO

Язык: Английский

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Air‐Stable Manganese NNS Pincer Complexes Enable Ketone Reduction at Room Temperature

ChemCatChem, Год журнала: 2024, Номер 16(9)

Опубликована: Янв. 22, 2024

Abstract A series of air‐stable Mn complexes bearing NNS pincer ligands have been synthesized and fully characterized. The activity the as (transfer) hydrogenation catalysts was investigated in detail, a variety ketones (>20 examples) were converted to corresponding secondary alcohols at room temperature. synthetic applicability this class is demonstrated by tolerance several functional groups including halides, primary amines, nitriles, esters, nitro‐groups. Moreover, optimal catalytic system 5c displayed high chemoselectivity presence other reducible such alkynes. Competitive experiments with analogous bidentate NN complex 8 indicated decoordination hemilabile thioether‐moiety during formation catalytically active hydrido species.

Язык: Английский

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Asymmetric Transfer Hydrogenation of Ketones Improved by PNN–Manganese Complexes

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(17), С. 12318 - 12325

Опубликована: Авг. 15, 2024

Chiral manganese(I) complexes that contain carbocyclic-fused 8-amino-5,6,7,8-tetrahydroquinolinyl groups are appended with distinct para-R substituents have proven to be effective catalysts in the asymmetric transfer hydrogenation (ATH) of a wide range ketones (48 examples). Notably, Mn2 proved most productive catalyst, allowing an outstanding turnover number 8300 catalyst loadings as low 0.01 mol %. Furthermore, this catalytic protocol shows considerable promise for applications synthesis chiral drugs such Lusutrombopag.

Язык: Английский

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